Production of gamma aceto propyl ether



' Patented Dec. 23, 1941 PRODUCTION OF GAIWMA ACETO PROPYL ETHER JosephR. Stevens, Plainfield, and Gustav A.

Stein, Elizabeth, N. J., assignors, by mesne assignments, to ResearchCorporation, New York, N. Y., a corporation of New York No Drawing.Application September 27, 1939, Serial No. 296,804

2 Claims.

This invention relates to the production of 'y aceto propyl ether, andhas for its objects the provision of this ether and a simple andeffective method of making it. I

It has been found that, when 7 aceto propyl alcohol is halogenated, theresulting 'y halogen 'y aceto propyl alcohol often reacts spontaneouslywith itself to form 7 halogen 'y aceto propyl ether. In accordance withthe present invention, the unhalogenated 'y aceto propyl ether isproduced and the thus formed ether may be treated with a halogen, ifdesired. 7 halogen 'y aceto propyl ether and the related halogenatedalcohol are useful in the preparation of thiazole derivatives which maybe used in the production of synthetic vitamin B1.

The above mentioned and other objects and features of the invention willbe apparent from the following detailed description of a specificexample thereof;

100 cc. of 'y aceto propyl alcohol, containing a drop of concentratedhydrochloric acid to speed up the reaction, were distilled several timesat 10 mm. pressure and in each case the fraction boiling at 105 to 115C. was collected. These fractions were combined and fractioned at 10 mm.pressure, giving a product boiling at 110 to 112 C. at this pressure.This product .was 7 aceto propyl ether. Calcd. for C1oH1sO3; MW 186;0:64.57; H=9.75. Found; MW 182 (dioxane); C=64.28; H=9.'79. d =0.0968; N1.4435.

'y aceto propyl ether is readily and quickly hydrolized by means of asmall amount of water into 7 aceto propyl alcohol. Since 7 aceto propylalcohol assumes several tautomeric forms, there are likewise severalpossible structures for 'y aceto propyl ether.

Thus, the structural formula of 'y aceto propyl alcohol may be writtenas follows:

0 HgQ-J'B-C Hz-CHx -C [hOH (ketonic form),

I OH HzC( J=CHCHzCH2OH (cnolic form), and

- II 011 HsC--CEz-CH:CH1 (innor other, loctono ring, or totrahy- 0droiurano form).

III

It is probable that any solution of this product contains some or all ofthese forms in equilibrium. The above outlined ketonic form undoubtedlyis in tautomeric equilibrium with the enolic form of the molecule. Thesetautomeric forms are, however, so readily interconvertible, in harmonywith, enol-keto tautomers in general, that for the sake of simplicitythe enolic forms will be ignored in the following discussion.

The possible structural formula of 'y aceto propyl ether may bepresented as follows:

CHaCO CHaCli2CH2O-CIlzCiiaClIzC O (7 Ha CHI-CHI CHaCOCHaCHaCHr-O- H:

2. The method of making 7 aceto propyl ether which comprises distilling'y aceto propyl alcohol at a temperatureof about to 112 C. and at apressure of about 10 mm. of mercury.

JOSEPH R. STEVENS. GUSTAV A. STEIN.

